Photographic materials containing n-substituted phthalimide compounds



UnitedStates atent Q PHOTOGRAPHIC MATERIALS CONTAINING: N- SUBSIITUTEDPHTHALIMIDE COMPOUNDS Karl Otto Gauguin, and David WilliamCrichtonRamsay, 'Mahchest'en'En'gland, assignors to lmpen'al Chemical IndustriesLimited, London, England, a corporation of Great Britain No Drawing.Application October 30, 1956 Serial No. 619,131

Claims priority, application Great Britain October 19, 1956 4 Claims.(Cl. 96- -56) This invention relates to photographic materials and moreparticularly to light-sensitive photographic materials containingdevelopers.

In the usual commercial process for developing exposed photographicmaterials, the photographic materials are passed through a tankcontaining the developer insolution. With repeated use of the developersolution, the concentration of the developer falls so that theprocessing conditions vary and it is eventually necessary to add newdeveloper to the tank. Also when multilayer photographic materials aredeveloped in this Way, the developer solution has to ditluse through theupper layers of the photographic materials before it can reach the lowerlayers so that an' even development of the various layers cannot'beachieved. For example with a photographic mate- I rial containing threedilierently sensitised gelatino silver halide emulsion layers, correctdevelopment of the bottom layer can only be obtained by having a highconcentration of developer in the developer solution, but under theseconditions there is a tendency forthe top layer to be over-developed.

Various suggestions have been made to overcome these dilficulties. Forexample, it has been proposed to incorporat'e' in the light-sensitiveemulsion layers certain developers, or mixtures of developers withcertain stabilisers, and, after exposure, todevelop the emulsion layerswith aqueous alkali but no such process has yet proved satisfactory incommercial practice.

We havenow found that certain substituted phthalimides, as hereinafterdefined, can be incorporated in gelatino-silver halide emulsion layers,and that the emulsion layers, after exposure to light can be developedby treatment with an alkaline solution of hydroxylamine or hydrazinewhich diffuses readily into the emulsion layers of a multilayermaterial.

According to our invention we provide a light sensitive gelatino-silverhalide emulsion layer which contains a substituted phthalimide of theformula R1 C i 1 RI \C O J wherein R and R are substituted orunsubstituted alkyl radicals or R and R may be joined together or eachor both joined to the benzene ring to form with the nitrogen atom aheterocyclic ring, X is hydrogen, an alkyl, substituted alkyl, alkyloxy,substituted alkyloxy, amino or substituted amino radical, and Y is asolubilising group, and wherein the benzene nuclei may carrysubstituents.

The solubilising group may be for example a carboxylic or sulphonic acidgroup or a salt of one of these, for example an alkali metal or ammoniumsalt.

The substitutedphthalimidea may- :be made-iby.1-.-heating.-.

an amine pf the formula t a an,

wherein R R and X have the meaning given above and thephenyl nucleus maycarry further.substituents,,with1: phthalic anhydride or a substitutedphthalic anhydrideg.. and, where both the amine and;phthalicranhydride-are groups, further treatingthe free from watersolubilising product to introduce a water solubilisinggroupr As examplesof the substituted phthalimides which may be used inour invention theremay be mentioned the compound made by condensing -4-diethylaminoanilinewith trimellitic anhydride for example by heating the reagentstogetherin boiling glacial acetic acid for 3 hours),the corresponding.aminocompound (X=Nl-l )"formed by nitration and. reduction,-thecompound made by; con- (lensing.4-amino=3 ethoxy-N:N-diethylanilineor-4-amino 3-methyl-N:N-diethylaniline- .with trimellitic anhydride orby condensing.4-diethylaminoaniline or- 4-amino-3-thoxy-NzN-diiethyl'aniline, ,with, 4-sulphophthalic an hydride.

Ina preferred form of our invention the gelatinosilver halideiemulsionnlayer also contains a ,colour coupler.

The emulsions vused .for forming -the-layers ofounirb; vention may bemade by simply.,mixing;an- .aqueousisolu tion or dispersion of thesubstituted phthalim de with a normal gelatino-silver halide emulsiqnprepared in thre known manner and if desiredadding one. onmore sen-1:

least one of the layersis a gelatinoe'silver. halide emulsion layercontaining a substituted phthalimide as hereinbefore-- defined, forms afurther feature of our invention.

Photographic materials containing the light-sensitive emulsion layers ofour invention may be exposed to light in the normal way and thendeveloped with an alkaline solution containing hydroxylamine orhydrazine and this process of development forms a further feature of ourinvention. If desired other adjuvants for example sodium sulphite andpotassium bromide may be added to the developer solution. The materialmay then be fixed and, when the emulsion layer contains a colourcoupler, the developed silver may be bleached.

The invention is illustrated but not limited by the following example inwhich the parts are by weight:

Example parts of a gelatin-silver iodo-bromide emulsion containing 7.25%of gelatine, 3.35% of silver bromide and 0.05 of silver iodide arestirred and there are added 3 parts of a 0.05% solution in methanol ofbis (3 ethyl 5 phenyl benzoxazole 2-) 9-ethy1trimethineyanine iodide(the iodide of the green sensitising dyestuit Rl340 described inB.I.O.S. Final Report No. 1355, page 86). The mixture is stirred at 40C. for 20 minutes and there are then added 24 parts of a 5% aqueoussolution of the sodium salt of 4- (omega-cyan0-acetyl)-oetadecenyl-succinanilide (the colour coupler K6 Parts Sodiumsulphite, anhydrous 1 Hydroxylamine hydrochloride 2 Sodium carbonate,anhydrous 30 Potassium bromide 0.5

Water to make up to 1,000 parts. 7

The paper is washed and then transferred to a stop bath of the followingcomposition:

. Parts Sodium thiosulphate 200 Sodium sulphite, anhydrous 2 Sodiumacetate Glacial acetic acid 10 Water to make up to 1,000 parts.

The paper is washed and the developed silver is bleached and fixed in asolution of the following composition:

Parts Ferric salt of ethylenediamine-tetra-acetic acid 20 Sodiumcarbonate, anhydrous 2 Sodium salt of ethylenediamine-tetra-aceticacid..... 10 Sodium sulphite, anhydrous 4 Potassium bromide 10 Sodiumthiosulphate 100 Water to make up to 1,000 parts.

The paper is finally washed and dried.

What we claim is:

1. A light sensitive gelatino-silver halide emulsion which contains asubstituted phthalimide of the formula:

co 1 N@ N Y co wherein R and R are alkyl radicals, X is selected fromthe group consisting of alkyl, alkoxy and amino and Y is a solubilisinggroup selected from the class consisting of sulphonic and carboxylicacid groups.

2. A light sensitive gelatino-silver halide emulsion ac cording to claim1 which contains, in addition to the substituted phthalimide as definedin claim 1, a colour coupler capable of coupling with the oxidationproduct of a primary aromatic amino developer to form a dye.

3. A photographic material comprising a plurality of layers coated on asupport, at least one of said layers being a light sensitivegelatino-silver halide emulsion layer which contains a substitutedphthalimide of the formula:

1 oo N-QN Y RI/ \CO wherein R and R are alkyl radicals, X is selectedfrom the group consisting of alkyl, alkoxy and amino and Y is asolubilising group selected from the class consisting of sulphonic andcarboxylic acid groups, and which further contains a colour couplercapable of coupling with the oxidation product of a primary aromaticamino developer to form a dye.

4. A 'colour photographic process which comprises imagewise exposing tolight a light sensitive gelatino-silver halide emulsion which contains asubstituted phthalimide of the formula:

wherein R and R are allcyl radicals, X is selected from the groupconsisting of alltyl, alkoxy and amino and Y is a solubilising groupselected from the class consisting of sulphonic and carboxylic acidgroups, and subsequently developing with an alkaline solution of amember of the class consisting of hydroxylamine and hydrazine.

References Cited in the file of this patent UNITED STATES PATENTS2,137,785 Sanders-Dolgoruki et al. Nov. 22, 1938 2,478,400 Ielley et a1.Aug. 9, 1949 2,706,157 Sainsbury et al. Apr. 12, 1955 OTHER REFERENCESH. Bennett: Concise Chemical & Technical Dictionary, page 26, ChemicalPubl. Co., Inc., New York, N.Y., publishers (1947).

1. A LIGHT SENSITIVE GELATINO-SILVER HALIDE EMULSION WHICH CONTAINS ASUBSTITUTED PHTHALIMIDE OF THE FORMULA: